Brazed ceramic seal for batteries

ABSTRACT

This invention is a sealed battery case and a method for making it, including a brazed ceramic ring that separates the positive and negative ends of the battery while providing a leak-tight seal. A brazing material is used that comprises greater than 50% gold. The case is strong, and can be negative, neutral, or positive, withstanding more than 3.5 V vs. Li/Li + .

REFERENCE TO PRIOR FILED APPLICATIONS

[0001] This application is a Continuation-in-Part of copending application Ser. No. 10/222,283, filed Aug. 15, 2002, which is a Continuation-in-Part of copending application Ser. No. 09/774,450, filed Jan. 30, 2001, which claims priority to U.S. provisional application 60/179,764, filed Feb. 20, 2000; and is a Continuation-in-Part of co-pending application 09/842,790, filed Apr. 25, 2001, which claims priority to U.S. provisional application 60/199,893, filed Apr. 26, 2000, the entirety of each of which is hereby incorporated herein by reference.

TECHNICAL FIELD

[0002] This invention relates to brazed ceramic seals for use in electrochemical storage batteries.

BACKGROUND

[0003] A chemical battery case may act to prevent the positive and negative output devices from coming into contact, i.e., shorting. The battery case in its entirety also functions to contain and prevent leakage of battery materials such as an electrolyte. Moreover, the battery case itself must provide for mechanical strength to contain pressures originating from within the battery as well as to provide the mechanical strength for ordinary handling of the battery.

SUMMARY

[0004] The invention includes a brazed ceramic ring that separates the positive and negative ends of the battery while providing a leak-tight seal. The ceramic preferably comprises alumina, zirconia, tetragonal zirconia, stabilized-zirconia, partially-stabilized zirconia, yttria-stabilized zirconia, magnesia-stabilized zirconia, ceria-stabilized zirconia, calcia-stabilized zirconia, and titania. The invention includes a brazing material that is greater than 50% gold, and preferably greater than 70% gold. The invention includes a case, which may be at a positive or negative potential or neutral. The material of the case is chosen to withstand this potential without corroding. The battery preferably employs a lithium battery chemistry, but is not so limited, and may alternatively employ other chemistries such as other alkali metal chemistries. As used herein, the terms “lithium batteries” and “lithium battery chemistries” include lithium ion batteries and lithium ion chemistries, respectively. For a negatively charged case, materials that have the requisite ability and corrosion resistance to be used as a negative element, such as a nickel, stainless, or commercially pure (CP) titanium, may be used. For a positively charged case, aluminum and certain alloys such as Ti-6Al-4V have the requisite ability and corrosion resistance to be used as a positive current carrying element where the battery's positive electrode exhibits more than 3.5 V vs. Li/Li⁺. Alternatively, the case may comprise stainless steel or other materials capable of withstanding even greater potentials, such as greater than 4.1 V vs. Li/Li⁺, and more preferably, greater than 4.3 V vs. Li/Li⁺.

BRIEF DESCRIPTION OF THE DRAWINGS

[0005]FIG. 1 shows a battery case having a case body, end caps, and a ceramic ring sandwich of the present invention;

[0006]FIG. 2 shows the ceramic ring sandwich with a ceramic ring between metal rings, and a gold-based braze between the ceramic ring and the metal rings.

DETAILED DESCRIPTION

[0007] The following description is of the best mode presently contemplated for carrying out the invention. This description is not to be taken in a limiting sense, but is merely made for the purpose of describing the general principles of the invention. The scope of the invention should be determined with reference to the claims.

[0008] A battery case 1, as shown in FIG. 1, provides for mechanical strength to contain pressures originating from within the battery as well as to provide the mechanical strength for ordinary handling of the battery. Titanium and its alloys, such as Ti-6Al-4V, which is principally titanium with 6% aluminum and 4% vanadium, with oxygen, nitrogen, carbon, hydrogen, and iron typically present as trace elements, have the desirable properties of titanium such as high strength for a relatively low weight. Battery case 1 may have a positively charged, negatively charged, or neutral case body 2, and a lid end cap 4 that is at a different potential from case body 2. The materials for the various portions of battery case 1 are chosen to withstand their respective potentials without corroding. Commercially pure (CP) titanium has the requisite ability and electro-activity to be used as a negative current carrying element; Ti-6Al-4V has the requisite ability and electro-activity to be used as a positive current carrying element where the battery's positive electrode exhibits more than 3.5 V vs. Li/Li⁺. Alternatively, the case may comprise stainless steel or other materials capable of withstanding even greater potentials, such as greater than 4.1 V vs. Li/Li⁺, and more preferably, greater than 4.3 V vs. Li/Li⁺, which may correspond to a battery voltage of greater than 3.6 V. A body end cap 3, which seals the bottom of the case body 2, comprises a material that is also chosen according to its potential.

[0009] A ceramic ring sandwich 20 is shown in FIGS. 1 and 2. First looking at FIG. 2, the ceramic ring 21 is brazed by the gold alloy braze 24 to two rings 22 and 23, the materials of which are chosen according to their potential. For a case body 2 that is positively charged, the case body 2, body end cap 3, and ring 22 comprise materials that can withstand a positive potential, such as Ti-6Al-4V, Al, or stainless steel (SS); and ring 23 comprises materials that can withstand a negative potential, such as SS, Cu, CP titanium, alloys thereof, Fe, Ni-plated Fe, Ni, and certain alloys thereof. For a case body 2 that is negatively charged, the case body 2, end cap 3, and ring 22 comprise materials that can withstand a negative potential, such as CP titanium, Cu, Fe, Ni-plated Fe, Ni, and SS; and ring 23 comprises materials that can withstand a positive potential, such as Al, SS, and certain titanium alloys, including Ti-6Al-4V and Ti-3Al-2.5V.

[0010] The gold alloy braze 24 is one that contains more than 50% gold by weight, and preferably more than 70% gold by weight. A specific type of gold alloy braze 24 is 96.4% gold, 3.0% nickel, and 0.6% titanium. Some trace elements may be present with a corresponding slight adjustment in the composition percentages. Like all of the materials of the battery case, the braze is chosen so that it can stand up to the electrochemical conditions inside the battery with which it will come in contact. The ceramic ring 21 preferably comprises aluminum oxide (alumina), zirconium oxide (zirconia), zirconium oxide with 3% yttrium (yttria-stabilized zirconia), titania, stabilized-zirconia, partially-stabilized zirconia, tetragonal zirconia, magnesia-stabilized zirconia, ceria-stabilized zirconia, and calcia-stabilized zirconia.

[0011] Returning to FIG. 1, the ceramic ring sandwich 20 is placed on the open end of the case body 2 with ring 22 toward the case body 2. Ring 22 is then laser welded to the case body 2. Subsequently, a lid end cap 4, comprising a material chosen according to its potential, is welded, preferably laser welded, to ring 23 of the ceramic ring sandwich 20.

[0012] The thicknesses 25, 26, and 27 of the ceramic and metal rings are preferably greater than 1 mm to facilitate welding and prevent shorting.

[0013] Methods of assembly for the ceramic ring sandwich 20 include brazing together a sheet of ceramic material between a sheet of titanium and titanium alloy Ti-6Al-4V and then laser cutting a shape to fit the end of a given battery case. The sandwich can be cut into almost any desired geometrical shape. Another method is cutting out the ceramic ring 21 and the titanium alloy Ti-6Al-4V ring 22 and the titanium ring 23 separately and brazing the pieces together.

[0014] Typically, once the ceramic sandwich 20 is welded to the case body 2, the battery electrodes (not shown) can be inserted into the case body 2 and a feedthrough (not shown) inserted through a hole 5 formed in the lid end cap 4. Alternatively, the lid end cap 4 may not have a hole formed therein and may itself serve as the opposite terminal without the use of a feedthrough, as described in copending application Ser. No. 10/222,283. The feedthrough (not shown) is welded shut to provide a leak-tight seal. The battery 1 is filled with electrolyte (not shown) and laser welded closed on the body end cap 3. Tabs (not shown), which are connected to the positive electrode (not shown), can be folded out of the case and laser welded at the same time as the body end cap 3, as described in applications Ser. Nos. 09/842,790 and 10/222,283.

[0015] While the invention herein disclosed has been described by means of specific embodiments and applications thereof, numerous modifications and variations could be made thereto by those skilled in the art without departing from the scope of the invention set forth in the claims. For example, while the invention has been illustrated for a circular cylindrical case body and circular end caps, metal rings, and ceramic rings, it can be appreciated that the case body, end caps, and rings may be noncircular, and that manufacturing methods described herein lend themselves to other shapes. Furthermore, while the case body 2 has been described as having a body end cap 3 welded to seal it, in fact, the case body may be deep drawn with an integral bottom, or the body end cap 3 may be sealed to the case body 2 using other means known in the art. 

We claim:
 1. A brazed ceramic ring sandwich comprising: a first ring comprising ceramic material; a second ring comprising a first metal sealed to said first ring with a gold alloy braze; and a third ring comprising a second metal sealed to said first ring with said gold alloy braze; wherein said gold alloy braze has a gold content of more than 50 wt %.
 2. The brazed ceramic ring sandwich of claim 1 wherein said ceramic material is selected from the group consisting of: alumina, zirconia, tetragonal zirconia, stabilized-zirconia, partially-stabilized zirconia, yttria-stabilized zirconia, magnesia-stabilized zirconia, ceria-stabilized zirconia, calcia-stabilized zirconia, and titania.
 3. The brazed ceramic ring sandwich of claim 1 wherein said gold alloy braze has a gold content of more than 70 wt %.
 4. The brazed ceramic ring sandwich of claim 1 wherein said gold alloy braze comprises 96.4% gold, 3.0% nickel, and 0.6% titanium.
 5. The brazed ceramic ring sandwich of claim 1 wherein at least one of said second and third rings comprises a material chosen from the group consisting of: Ti-6Al-4V, Ti-3Al-2.5V, Al, and stainless steel.
 6. The brazed ceramic ring sandwich of claim 1 wherein said at least one of said second and third rings comprises a material chosen from the group consisting of: CP titanium, alloys thereof, Fe, Ni-plated Fe, Ni, nickel alloy, SS, and Cu.
 7. The brazed ceramic ring sandwich of claim 1 wherein said second ring comprises a material chosen from the group consisting of: Ti-6Al-4V, Ti-3Al-2.5V, Al, and stainless steel, and wherein said third ring comprises a material chosen from the group consisting of: CP titanium, Fe, Ni-plated Fe, Ni, nickel alloy, SS, and Cu.
 8. The brazed ceramic ring sandwich of claim 1 wherein said rings are circular.
 9. The brazed ceramic ring sandwich of claim 1 wherein said rings are noncircular.
 10. A battery case comprising: a case body having a sealed end; an end cap sealed to said case body using the brazed ceramic ring sandwich of claim 1; wherein said third ring of said brazed ceramic ring sandwich is welded to said case body, and wherein said second ring of said brazed ceramic ring sandwich is welded to said end cap.
 11. The battery case of claim 10 wherein said third ring of said brazed ceramic ring sandwich is welded to said case body with a laser weld.
 12. The battery case of claim 10 wherein said second ring of said brazed ceramic ring sandwich is welded to said end cap with a laser weld.
 13. The battery case of claim 10 wherein said ceramic material is selected from the group consisting of: alumina, zirconia, tetragonal zirconia, stabilized-zirconia, partially-stabilized zirconia, yttria-stabilized zirconia, magnesia-stabilized zirconia, ceria-stabilized zirconia, calcia-stabilized zirconia, and titania.
 14. The battery case of claim 10 wherein said gold alloy braze has a gold content of more than 70 wt %.
 15. The battery case of claim 10 wherein said gold alloy braze comprises 96.4% gold, 3.0% nickel, and 0.6% titanium.
 16. The battery case of claim 10 wherein said case body and said third ring comprise the same metal.
 17. The battery case of claim 10 wherein said end cap and said second ring comprise the same metal.
 18. The battery case of claim 10 wherein said second ring comprises a material chosen from the group consisting of: CP Ti, alloys thereof, Ti-6Al-4V, Ti-3Al-2.5V, and stainless steel.
 19. The battery case of claim 10 wherein said third ring comprises a material chosen from the group consisting of: CP titanium, alloys thereof, Ti-6Al-4V, Ti-3Al-2.5V, and stainless steel.
 20. A battery comprising: the battery case of claim 10; electrodes housed in said battery case; and electrolyte contained within said battery case.
 21. The battery of claim 20 wherein said battery case comprises a positive current carrying element of said battery.
 22. The battery of claim 21 wherein said positive current carrying element exhibits more than 3.5 V vs. Li/Li⁺.
 23. The battery of claim 21 wherein said positive current carrying element exhibits more than 4.1 V vs. Li/Li⁺.
 24. The battery of claim 21 wherein said positive current carrying element exhibits more than 4.3 V vs. Li/Li⁺.
 25. The battery of claim 20 wherein said battery is a lithium battery.
 26. The battery of claim 20 wherein said end cap is negatively charged.
 27. The battery of claim 20 wherein said battery case comprises a negative current carrying element of said battery.
 28. The battery of claim 20 wherein said end cap is positively charged.
 29. A battery case comprising: a case body having a sealed end; an end cap sealed to said case body using the brazed ceramic ring sandwich comprising: a first ring comprising ceramic material; a second ring comprising a first metal sealed to said first ring with a gold alloy braze; and a third ring comprising a second metal sealed to said first ring with said gold alloy braze; wherein said gold alloy braze has a gold content of more than 50 wt%; wherein said third ring of said brazed ceramic ring sandwich is welded to said case body; and wherein said second ring of said brazed ceramic ring sandwich is welded to said end cap.
 30. A battery comprising: a battery case comprising: a case body having a sealed end; an end cap sealed to said case body using a brazed ceramic ring sandwich comprising: a first ring comprising ceramic material; a second ring comprising a first metal sealed to said first ring with a gold alloy braze; and a third ring comprising a second metal sealed to said first ring with said gold alloy braze; wherein said gold alloy braze has a gold content of more than 50 wt %; wherein said third ring of said brazed ceramic ring sandwich is welded to said case body; and wherein said second ring of said brazed ceramic ring sandwich is welded to said end cap; electrodes housed in said battery case; and electrolyte contained within said battery case.
 31. The battery of claim 30 wherein said battery case comprises a positive current carrying element of said battery.
 32. The battery of claim 31 wherein said positive current carrying element exhibits more than 3.5 V vs. Li/Li⁺.
 33. The battery of claim 31 wherein said positive current carrying element exhibits more than 4.1 V vs. Li/Li⁺.
 34. The battery of claim 31 wherein said positive current carrying element exhibits more than 4.3 V vs. Li/Li⁺.
 35. The battery of claim 30 wherein said battery is a lithium battery.
 36. The battery of claim 30 wherein said end cap is negatively charged. 